Ligand Protonation Triggers H2 Release from a Dinickel Dihydride Complex to Give a Doubly "T"-Shaped Dinickel(I) Metallodiradical.

The dinickel(II) dihydride complex (1K ) of a pyrazolate-based compartmental ligand with ß-diketiminato (nacnac) chelate arms (L- ), providing two pincer-type {N3 } binding pockets, has been reported to readily eliminate H2 and to serve as a masked dinickel(I) species. Discrete dinickel(I) complexes (2Na , 2K ) of L- are now synthesized via a direct reduction route. They feature two adjacent T-shaped metalloradicals that are antiferromagnetically coupled, giving an S=0 ground state. The two singly occupied local d x 2 - y 2 type magnetic orbitals are oriented into the bimetallic cleft, enabling metal-metal cooperative 2 e- substrate reductions as shown by the rapid reaction with H2 or O2 . X-ray crystallography reveals distinctly different positions of the K+ in 1K and 2K , suggesting a stabilizing interaction of K+ with the dihydride unit in 1K . H2 release from 1K is triggered by peripheral γ-C protonation at the nacnac subunits, which DFT calculations show lowers the barrier for reductive H2 elimination from the bimetallic cleft.

A Review of Density Functional Models for the Description of Fe(II) Spin-Crossover Complexes.

Spin-crossover (SCO) materials have for more than 30 years stood out for their vast application potential in memory, sensing and display devices. To reach magnetic multistability conditions, the high-spin (HS) and low-spin (LS) states have to be carefully balanced by ligand field stabilization and spin-pairing energies. Both effects could be effectively modelled by electronic structure theory, if the description would be accurate enough to describe these concurrent influences to within a few kJ/mol. Such a milestone would allow for the in silico-driven development of SCO complexes. However, so far, the ab initio simulation of such systems has been dominated by general gradient approximation density functional calculations. The latter can only provide the right answer for the wrong reasons, given that the LS states are grossly over-stabilized. In this contribution, we explore different venues for the parameterization of hybrid functionals. A fitting set is provided on the basis of explicitly correlated coupled cluster calculations, with single- and multi-dimensional fitting approaches being tested to selected classes of hybrid functionals (hybrid, range-separated, and local hybrid). Promising agreement to benchmark data is found for a rescaled PBE0 hybrid functional and a local version thereof, with a discussion of different atomic exchange factors.